Hydrolyzed polyvinyl acetate resin hair sprays



United States Patent 3,417,180 HYDROLYZED POLYVTNYL ACETATE RESIN HAIR SPRAYS Julius Sirota, South Plainfield, and Albert L. Micchelli, Middletown, N.J., assignors to National Starch and Chemical Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Jan. 18, 1966, Ser. No. 521,420 3 Claims. (Cl. 424-47) ABSTRACT OF THE DISCLOSURE An aerosol formulation suitable for use as a hair spray lacquer comprising an organic solvent solution of a hydrolyzed polyvinyl acetate resin hydrolyzed to the extent that from about to 60% of its acetate groups are converted into hydroxyl groups, in admixture with an aerosol propellant therefor.

This invention relates to the preparation of hair fixing compositions especially suitable for use in aerosol formulations and, more particularly, to the film forming, polymeric substances contained therein.

In order to be highly effective in aerosol hair spray formulations, the film forming polymeric components utilized therein as well as the films they deposit must meet a rigid set of requirements. Thus, the resulting films should be flexible and yet have sufiicient strength and elasticity; they should adhere well to hair so as to avoid dusting or flaking off when the hair is subjected to varying stresses; they should readily allow the hair to be recombed; they should maintain their non-tacky state despite humid conditions; they should be clear, transparent and glossy and should maintain this clarity on aging; they should possess good antistatic properties; and, they should be easily removable by the use of water and either soap or shampoo. In addition, the film forming polymeric components should be readily soluble in the solvents which are commonly used in these formulations; they should be miscible with aerosol propellants; and they should show little or no tendency to interact with the perfumes or other optional components utilized in hair spray lacquer formulations. Finally, the resulting resin-solvent systems should have a viscosity range which permits them to be uniformly sprayed; they should be stable so as to avoid the initiation of spray can corrosion; and they should, preferably, be capable of being produced in an efficient and economical manner.

Needless to say, many polymeric systems have been utilized in an attempt to meet these stringent requirements. Among these are included: polyvinylpyrrolidone, copolymers of N-vinyl pyrrolidone with vinyl acetate, 5,5-dimethyl hydantoin-formaldehyde resins, copolymers of methyl vinyl ethers and maleic half esters and terploymers of N-vinyl pyrrolidone, acrylate ester and acrylic acid, etc. Though each of these systems has met at least some of the above cited requirements, none has exhibited all of these required characteristics to an optimum degree.

It is, thus, the object of this invention to produce hair spray formulations which exhibit all of the above described properties. It is a further object to provide film forming polymeric components for utilization therein which are both soluble in anhydrous alcohols as well as compatible with the halogenated hydrocarbons ordinarily employed as aerosol propellants; this combination of properties making these polymeric components particularly valuable for use in these hair spray lacquer formulations. Various other objects and advantages of this in- Patentedl Dec. 17, 1968 "ice vention will become apparent to the practitioner from the following detailed description thereof.

We have now found that by utilizing partially hydrolyzed polyvinyl acetate, as hereinafter described, as the polymeric, film forming component of the hair spray formulations of this invention, all of the previously described requirements for an effectivehair spray formulation are met. Thus, the specified partially hydrolyzed polyvinyl acetates are soluble in anhydrous solvents, are completely compatible with aerosol propellants and show little or no tendency to interact with perfumes or other components of hair spray lacquer formulations. Furthermore, the films cast from organic solvent solutions of these polymers are clear and glossy, do not yellow upon aging, and possess the highly desirable properties of softness and flexibility. In addition, these films are readily removable from hair by the use of soaps and commercially available shampoos.

The partially hydrolyzed polyvinyl acetate applicable for use in the process of this invention are limited with regard to the molecular weight of the polyvinyl acetate bases utilized in their preparation as well as by the percent of acetate ester groups of the polyvinyl acetate bases which have been hydrolyzed to hydroxyl groups. Thus, expressing molecular weight in terms of intrinsic viscosity, the intrinsic viscosity, as determined in acetone at 30 C., of the applicable polyvinyl acetates should range from about 0.08 to 0.15, although the lower molecular weight polymers, i.e., those whose LV. ranges from about 0.08 to 0.12, are preferred. The use, in the preparation of the hydrolyzed polyvinyl acetates applicable for use in this invention, of polyvinyl acetates exhibiting intrinsic viscosities in excess of about 0.15 is undesirable since they tend to produce more viscous and less soluble products, while polyvinyl acetates exhibiting intrinsic viscosities falling below about 0.08 form products which are too soft and hygroscopic and thus generally unsuitable for use as hair spray binders.

It should be noted that it may also be possible to utilize hydrolyzed copolymers of vinyl acetate as the film forming bases of the novel hair spray formulations of this invention. Thus, for example, one may employ hydrolyzed copolymers of vinyl acetate with such monomers as cratonic acid, fumaric acid, itaconic acid, the C -C alkyl half esters of maleic and fumaric acids, acrylic acid and methacrylic acid.

The procedure utilized for hydrolizing the acetate ester groups of polyvinyl acetate are well known to those skilled in the art. Thus, the polyvinly acetate is usually dispersed in water and then refluxed in the presence of either acid or alkaline catalysts. For purposes of this invention, the use of partially hydrolyzed polyvinyl acetate which has been prepared by means of acidic hydrolysis with acidic catalysts such as p-toluenesulfonic acid is preferred because such partially hydrolyzed polyvinyl acetates are found to be lighter in color (less viscous, more stable, and more soluble than those prepared with alkaline catalysts. It should be noted that the percent hydrolysis can be readily controlled by simply altering one or more of the process variables utilized in the hydrolysis procedure such, for example, as the reaction time, the concentration of catalyst, or the concentration of water, etc.

In order to be applicable for use in preparing the products of this invention, the polyvinyl acetates should be hydrolyzed to the extent that from about 15 to 60% of their acetate groups are converted into hydroxyl groups. Products exceeding about 60% hydrolysis show little compatibility with either the anhydrous alcohol solvent or the halocarbon propellant, while products falling below about 15% hydrolysis are less Water sensitive and, therefore, more diflicult to remove from hair by conventional means, i.e., by washing and shampooing.

As previously mentioned, the other essential ingredients of the hair spray formulations of this invention are the solvent and the propellant. The preferred solvents are anhydrous alcohols such as ethanol and isopropanol. In addition to their solubility properties, the prime advantages of these anhydrous solvents are their ability to dry quickly and their minimal corrosive effect on the metal containers ordinarily utilized for these pressurized aerosol formulations.

Halogenated hydrocarbon aerosol propellants are well known to those skilled in the art. The commonly used propellants include trichlorofluoromethane and dichlorodifluoromethane as well as mixtures of the latter propellents. These propellants are readily miscible with the resin-alcohol solutions utilizedin this invention.

In general, the method for preparing the hair spray formulations of this invention merely involves admixing the partially hydrolyzed polyvinyl acetate with the anhydrous alcohol, adding any modifying agents whose presence may be desired, and thereupon, under pressure and lowered temperatures, combining the resulting solution with the selected aerosol propellant.

With regard to proportions, the final hair spray formulations typically contain a concentration of partially hydrolyzed polyvinyl acetate ranging from about 1 to 7%, by weight; a concentration of anhydrous solvent ranging from about 8 to 49%, by weight; and, a concentration of propellant ranging from about 50 to 80%, by weight. The presence of additional partially hydrolyzed polyvinyl acetate may possibly cause clogging of the aerosol container, while the presence of excess solvent increases the drying time and is, also economically undesirable. The latter proportions should, however, be considered as being merely illustrative inasmuch as it may well be possible to prepart operable formulations having concentrations of components which fall outside of the above suggested ranges.

Optional additives may be incorporateed into the hair spray formulations of this invention in order to modify certain properties thereof. Among these additives may be included: plasticizers such as glycols, phthalate esters, and glycerine; silicones which are use to increase water repellency; emollients, lubricants and penetrants such as lanolin compounds, ethylene oxide adducts, and polyoxyethylene chloesterol; and, perfumes. As previously noted, the partially hydrolyzed polyvinyl acetate resins show little or no tendency to interact with such additives.

The resulting hair spray formulations exhibit all of the characteristics required of such a product. Their films are transparent, glossy, flexible and strong. They possess good antistatic properties, adhere well to hair, are easily removed by soapy water or shampoos, allow the hair to be readily recombed, do not yellow on aging, and do not become tacky when exposed to high humidities. In addition, it should be noted that the primary resin solutions of this invention are equally as effective when utilized in hair-setting lotions, which are either aqueous or organic solvent based.

In the following examples, which further illustrate the embodiment of this invention, all parts given are by weight unless otherwise indicated.

This example illustrates a typical procedure for preparing the partially hydrolyzed polyvinyl acetates which are applicable for use in the preparation of the novel products of this invention.

EXAMPLE I The following ingredients were introduled into a vessel p-Toluenesulfonic acid 1.6

Under agitation, the above ingredients were refluxed at a temperature of 212 F. for a period of 1.5 hours at which time a clear solution resulted. The latter solution was then refluxed for an additional 1.5 hours. The catalyst was neutralized by the addition of 0.36 part of sodium hydroxide and the resulting product was then steam distilled for about 3 hours while the internal temperature of the system was raised to 250 F. This distillation pro- EXAMPLE II This example illustrates the preparation of a hair spray formulation typical of this invention utilizing the 37% hydrolyzed polyvinyl acetate whose preparation Was described in Example I, hereinabove.

A solution consisting of one part of the 37% hydrolyzed polyvinyl acetate in 5 parts of anhydrous ethanol was prepared. Thereafter, 24 parts of additional ethanol were added so as to obtain a completely clear solution whereupon 70 parts of a 60:40 pro ellant mixture of tr1- chlorofluoromethane and dichlorodifiuoromethane was added to the resin solution and the resulting miscible system was charged into an aerosol container.

When utilized, the resulting hair spray deposited a film which was characterized by its clarity, gloss, softness and flexibility. It served to hold the desired hair style in place while also allowing for its recombing. Of great significance was the fact that it was readily removed from the hair by the use of a conventional shampoo.

It may also be noted that on standing at a temperature of F. for a period of six Weeks, no corrosion was found upon examining the interior of the container.

EXAMPLE HI This example illustrates the excellent properties exhibited by a variety of the partially hydrolyzed polyvinyl acetates utilized in preparing the products of this invention. It further illustrates the advisability of utilizing partially hydrolyzed polyvinyl acetates which have been hydrolyzed to the extent of from about 15 to 60% of their available acetate groups.

Utilizing the general procedure set forth in Example I, hereinabove, partially hydrolyzed polyvinyl acetates were prepared exhibiting varying degrees of hydrolysis. The resulting partially hydrolyzed polyvinyl acetates were then submitted to the following test procedures:

Water solubility-Wet films having a thickness of 0.9 mil were cast from 30%, by Weight, ethanol solutions of the respective polymers. Thereafter, 0.5 part of the dried films thus obtained were shaken for 30 minutes in a glass cylinder containing 20 parts of water. Observations were made as to whether the films were totally soluble, partially soluble, totally insoluble or dispersible in the water. Complete dispersibility is sufiicient to show the film will be sufiiciently hydrated and softened by water so as to be easily removed from hair by the use of water with shampoo.

Alcohol solubility.Under agitation, 40 parts of the respective partially hydrolyzed polyvinyl acetates were admixed with 60 parts of anhydrous ethanol. Acceptable solubility properties were indicated by the resulting appearance, after thorough agitation, of clear or relatively clear solutions which were free of insolubles.

Propellant miscibility.This property was determined by admixing 20 parts of a 3%, by weight, solution of the partially hydrolyzed polyvinyl acetate in anhydrous ethanol with 33 parts of a 60:40 propellant mixture of trichlorofluoromethane and dichlorodifluoromethane. Ob-

servations were made for clarity, haziness, or precipitation.

Flm hardness.A series of films having a wet thickness of 1.5 mils were cast on glass plates from 30%, by weight, solutions of the polymers in anhydrous ethanol. These films were dried for 24 hours at a temperature of 72 F. and a relative humidity of 55%. The surface hardness of these films were then tested using a Sward hardness rocker. This device measures surface hardness and, indirectly, flexibility (i.e. those materials which are soft are also generally flexible). The results of the hardness tests were rated on a numerical scale of from to 100. Thus, a glass plate gives a Value of 100, while a value of 0 implies a surface which is so soft as to be tacky.

Formulations #1 to #3 were found to be completely clear while Formulations #4 and #5 showed varying amounts of haziness. Despite these slight differences, all of these formulations provided transparent, glossy, flexible films which firmly adhered to hair but which were, nonetheless, readily removed by means of conventional shampooing. In addition, the films derived from these formulations retained their original nontacky state, were resistant to the build-up of electrostatic charges, and maintained their effective holding power despite frequent combing.

Summarizing, it is thus seen that this invention provides for the preparation of novel hair spray formulations which are characterized by their excellent holding power The results of the various tests are described in the fol- 5 as well as by the fact that they are readily removable.

lowing table:

Variations may, of course, be made in proportions,

The data summarized above thus serves to illustrate the complete alcohol solubility and propellant miscibility of 3 EXAMPLE IV This example illustrates the preparation of hair spray formulations typical of this invention wherein various modifying additives have been included.

The formulations described in the table below were all prepared utilizing the procedure set forth in Example II, hereinabove. The modifying agents were added to the procedures, and materials without departing from the scope of this invention which is defined by the following claims.

We claim:

1. An aerosol formulation suitable for use as a hair spray lacquer comprising an organic solvent solution of an effective amount of a hydrolyzed polyvinyl acetate resin, hydrolyzed to the extent that from about to 60% of its acetate groups are converted into hydroxyl groups, in admixture with an aerosol propellant therefor, said polyvinyl acetate resin having an intrinsic viscosity, in acetone at C., in the range of from about 0.08 to 0.15.

2. The aerosol formulation of claim 1, wherein said organic solvent is anhydrous ethanol or isopropanol.

3. The aerosol formulation of claim 1 wherein the partially hydrolyzed polyvinyl acetate has a concentration ranging from 1 to 7%, by weight, the organic solvent has a concentration ranging from 8 to 49%, by weight, and the propellant has a concentration ranging from 50 to 85%, by weight. I

5 res1n-alcohol solutions prior to the addition of the pro- 4 pellant thereto.

Parts Components Form Form. Form. Form Form.

15% hydrolyzed polyvinyl acetate 5.0

34% hydrolyzed polyvinyl acetate hydrolyzed polyvinyl acetate... hydrolyzed polyvinyl acetate... 59% hydrolyzed polyvinyl acetate Anhydrous ethanol A 40:60 propellant mixture of triehlorofiuoromethane and dichlorodifluoromethane A 60:40 propellant mixture of trichloroiluoromethane and dichlorodifluoromethane Glycerine (plasticizer) Dibutyl plrtlialate (plastieizer). Silicone compound (water repellent) Isopropyl lanolate (lubricant)-... Polyoxyethylcne cholesterol (lubricant) Perfume 0.4

References Cited UNITED STATES PATENTS 3,144,391 8/1964 Goff 16787.l

ALBERT T. MEYERS, Primary Examiner.

VERA C. CLARKE, Assistant Examiner.

US. Cl. X.R. 

